This application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 2000-356086, filed Nov. 22, 2000, the entire contents of which are incorporated herein by reference.
1. Field of the Invention
The present invention relates to a silver halide color photographic lightsensitive material which improves the color reproduction and dye image stability, suppresses various stains, and increases the processing stability by using a pyrrolotriazole cyan coupler having a specific structure.
2. Description of the Related Art
It is well known that in silver halide color photographic lightsensitive materials, an aromatic primary amine-based color developing agent oxidized by using an exposed silver halide as an oxidizer reacts with couplers to form dyes such as indophenol, indoaniline, indamine, azomethine, phenoxazine, and phenazine, thereby forming images. This photographic scheme uses subtraction color processes and forms color images by yellow, magenta, and cyan dyes.
To form a cyan dye image, a phenol- or naphthol-based coupler is conventionally used. However, dyes formed from these couplers have unpreferable absorption in regions from yellow to magenta and hence deteriorate the color reproduction. So, solving this problem has been desired.
Especially in recent years, demands on so-called digital photography are increasing by which image information is converted into digital information, image processing is performed, and after that, a silver halide color photographic lightsensitive material is exposed on the basis of the information. In this digital photography, a silver halide color photographic lightsensitive material having a wide color reproduction range, in which formed dyes have no such unpreferable absorption as described above, is desired.
Also, reversal films are desired to have high saturation and a wide color reproduction range. However, a method which emphasizes the interlayer effect has drawbacks such as deterioration of the processing dependency. Therefore, it has been required to realize high saturation and wide color reproduction by couplers superior in hue.
As means for solving this problem, heterocyclic compounds as described in, e.g., U.S. Pat. Nos. 4,728,598 and 4,873,183 and European Patent Publication No. 0249453A2 have been proposed. Unfortunately, these couplers have fatal drawbacks such as low coupling activity and low dye image stability.
As couplers which have solved these problems, pyrrolotriazole couplers described in U.S. Pat. No. 5,256,526 and European Patent 0545300 have been proposed. Although these couplers are superior in hue and coupling activity, color photographic lightsensitive materials using these couplers have no sufficient dye image stability. So, the couplers must be further improved. Also, the couplers have the problem (so-called blix fading) that the color generation reduces by leuco conversion of a dye (a dye is partially decolored by reduction) during bleach-fixing. Additionally, diverse cyan stains are produced. Furthermore, conventionally known pyrrolotriazole cyan couplers produce a magenta stain with time when processed using formalin.
Moreover, in color reversal films, it is desired to shorten processing and to reduce the replenishment rate. The inventors of the present invention have studied these matters, and found that there was a problem that the decrease of cyan maximum density becomes larger in the case of also reducing the replenishment rate of the reversal solution in the reversal bath simultaneously with reducing the replenishment rate of the color developer. Further, this problem often becomes more serious in conventional pyrrolotriazole cyan couplers than in phenol-type cyan couplers conventionally used, thus this problem must be solved.
It is, therefore, an object of the present invention to provide a silver halide color photographic lightsensitive material
1) which improves the color reproduction and dye image stability by the use of a novel pyrrolotriazole cyan coupler having a specific structure, which is useful as coupler in a silver halide color photographic lightsensitive material, and
2) which reduces a cyan stain produced by the reaction with a residual color developing agent, causes blix fading little, minimizes a magenta stain, and improves the processing stability.
The present inventors extensively studied 2-position substituents and split-off groups of pyrrolotriazole-based couplers having good hue, and have found that the above problems can be solved by a coupler, represented by the following formula, having an entirely new structure conventionally unknown. That is, the object of the present invention is achieved by the following means.
(1) A silver halide color photographic lightsensitive material comprising at least one layer on a support, wherein the at least one layer contains a coupler represented by formula (I) below. 
In formula (I), X represents a member selected from the group consisting of a hydrogen atom, halogen atom, 1- to 32-carbon alkoxy group, 6- to 32-carbon aryloxy group, 1- to 32-carbon alkylthio group, 6- to 32-carbon arylthio group, 2- to 32-carbon heterocyclic thio group, 2- to 32-carbon alkoxycarbonyloxy group, 7- to 32-carbon aryloxycarbonyloxy group, 1- to 32-carbon carbamoyloxy group, 3- to 32-carbon heterocyclic carbonyloxy group, 2- to 30-carbon alkylcarbonyloxy group, 7- to 30-carbon arylcarbonyloxy group, and 2- to 32-carbon, 5- or 6-membered nitrogen-containing heterocyclic group that bonds to the coupling active position with a nitrogen atom.
Each of R1 and R2 represents an electron-attracting group having a Hammett""s substituent constant "sgr"p value of not less than 0.20, the sum of the "sgr"p values of R1 and R2 being not less than 0.65.
R3 represents a member selected from the group consisting of a substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, substituted or nonsubstituted aryl group, and substituted or nonsubstituted heterocyclic group; and R4 represents a member selected from the group consisting of a hydrogen atom, substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, substituted or nonsubstituted aryl group, substituted or nonsubstituted acyl group, substituted or nonsubstituted alkoxycarbonyl group, substituted or nonsubstituted aryloxycarbonyl group, and substituted or nonsubstituted carbamoyl group. Alternatively, R3 and R4 may bond together to form a ring structure.
Each of R11 to R15 independently represents a hydrogen atom or a substituent, and at least one of R11 to R15 represents xe2x80x94(L1)xe2x80x94(L2)nxe2x80x94R, wherein L1 represents xe2x80x94CONHxe2x80x94, xe2x80x94NHCONHxe2x80x94, xe2x80x94NHCOOxe2x80x94, xe2x80x94NHCOxe2x80x94, xe2x80x94OCONHxe2x80x94, xe2x80x94NHxe2x80x94, xe2x80x94NRXxe2x80x94, xe2x80x94COOxe2x80x94, xe2x80x94OCOxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94NHSO2xe2x80x94, xe2x80x94SO2NHxe2x80x94, or xe2x80x94CH2xe2x80x94 (wherein the left side of each group binds to the benzene ring of formula (I)), L2 represents xe2x80x94CH2CH2Oxe2x80x94 or xe2x80x94CH2CONHxe2x80x94 (wherein the left side of each group binds to L1).
R represents an 8- to 40-carbon, branched-chain or straight-chain, nonsubstituted alkyl group. RX represents an alkyl group.
n represents 0, when L1 is a group other than xe2x80x94Oxe2x80x94; n represents 1, when L1 is xe2x80x94Oxe2x80x94 and L2 is xe2x80x94CH2CONHxe2x80x94; and n represents an integer from 0 to 10, when L1 is xe2x80x94Oxe2x80x94 and L2 is xe2x80x94CH2CH2Oxe2x80x94.
Two or more groups of R11 to R15 are not simultaneously branched-chain or straight-chain, nonsubstituted alkyl groups.
(2) A silver halide color photographic lightsensitive material comprising at least one layer on a support, wherein the at least one layer contains a coupler represented by formula (II) below. 
In formula (II), X represents a member selected from the group consisting of a hydrogen atom, halogen atom, 1- to 32-carbon alkoxy group, 6- to 32-carbon aryloxy group, 1- to 32-carbon alkylthio group, 6- to 32-carbon arylthio group, 2- to 32-carbon heterocyclic thio group, 2- to 32-carbon alkoxycarbonyloxy group, 7- to 32-carbon aryloxycarbonyloxy group, 1- to 32-carbon carbamoyloxy group, 3- to 32-carbon heterocyclic carbonyloxy group, 2- to 30-carbon alkylcarbonyloxy group, 7- to 30-carbon arylcarbonyloxy group, and 2- to 32-carbon, 5- or 6-membered nitrogen-containing heterocyclic group that bonds to the coupling active position with a nitrogen atom.
Each of R1 and R2 represents an electron-attracting group having a Hammett""s substituent constant "sgr"p value of not less than 0.20, the sum of the "sgr"p values of R1 and R2 being not less than 0.65.
R3 represents a member selected from the group consisting of a substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, substituted or nonsubstituted aryl group, and substituted or nonsubstituted heterocyclic group; and R4 represents a member selected from the group consisting of a hydrogen atom, substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, substituted or nonsubstituted aryl group, substituted or nonsubstituted acyl group, substituted or nonsubstituted alkoxycarbonyl group, substituted or nonsubstituted aryloxycarbonyl group, and substituted or nonsubstituted carbamoyl group. Alternatively, R3 and R4 may bond together to form a ring structure.
Each of R11 to R15 independently represents a hydrogen atom or a substituent, and at least two of R11 to R15 represent branched-chain or straight-chain, nonsubstituted alkyl groups.
(3) A method of forming an image by using the silver halide color photographic lightsensitive material described in item (1).
(4) A method of forming an image by using the silver halide color photographic lightsensitive material described in item (2).
(5) A compound represented by formula (III) below: 
wherein
X represents a member selected from the group consisting of a hydrogen atom, halogen atom, 1- to 32-carbon alkoxy group, 6- to 32-carbon aryloxy group, 1- to 32-carbon alkylthio group, 6- to 32-carbon arylthio group, 2- to 32-carbon heterocyclic thio group, 2- to 32-carbon alkoxycarbonyloxy group, 7- to 32-carbon aryloxycarbonyloxy group, 1- to 32-carbon carbamoyloxy group, 3- to 32-carbon heterocyclic carbonyloxy group, 2- to 30-carbon alkylcarbonyloxy group, 7- to 30-carbon arylcarbonyloxy group, and 2- to 32-carbon, 5- or 6-membered nitrogen-containing heterocyclic group that bonds to the 5-position of the 1H-pyrrolo-[1,2-b][1,2,4]triazole ring with a nitrogen atom;
each of R1 and R2 represents an electron-attracting group having a Hammett""s substituent constant "sgr"p value of not less than 0.20, the sum of the "sgr"p values of R1 and R2 being not less than 0.65;
R3 represents a member selected from the group consisting of a substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, substituted or nonsubstituted aryl group, and substituted or nonsubstituted heterocyclic group, and R4 represents a member selected from the group consisting of a hydrogen atom, substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, substituted or nonsubstituted aryl group, substituted or nonsubstituted acyl group, substituted or nonsubstituted acy l group, substituted or nonsubstituted alkoxycarbonyl group, substituted or nonsubstituted aryloxycarbonyl group, and substituted or nonsubstituted carbamoyl group, or alternatively, R3 and R4 may bond together to form a ring structure; and
each of R11 to R15 independently represents a hydrogen atom or a substituent, and at least two of R11 to R15 represent branched-chain or straight-chain, nonsubstituted alkyl groups.
(6) The lightsensitive material described in item (1), wherein the lightsensitive material is a reversal film.
(7) The lightsensitive material described in item (2), wherein the lightsensitive material is a reversal film.
(8) A method of reducing a magenta stain by containing a coupler represented by formula (I) below in a silver halide color photographic lightsensitive material: 
wherein
X represents a member selected from the group consisting of a hydrogen atom, halogen atom, 1- to 32-carbon alkoxy group, 6- to 32-carbon aryloxy group, 1- to 32-carbon alkylthio group, 6- to 32-carbon arylthio group, 2- to 32-carbon heterocyclic thio group, 2- to 32-carbon alkoxycarbonyloxy group, 7- to 32-carbon aryloxycarbonyloxy group, 1- to 32-carbon carbamoyloxy group, 3- to 32-carbon heterocyclic carbonyloxy group, 2- to 30-carbon alkylcarbonyloxy group, 7- to 30-carbon arylcarbonyloxy group, and 2- to 32-carbon, 5- or 6-membered nitrogen-containing heterocyclic group that bonds to the coupling active position with a nitrogen atom;
each of R1 and R2 represents an electron-attracting group having a Hammett""s substituent constant "sgr"p value of not less than 0.20, the sum of the "sgr"p values of R1 and R2 being not less than 0.65;
R3 represents a member selected from the group consisting of a substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, substituted or nonsubstituted aryl group, and substituted or nonsubstituted heterocyclic group, and R4 represents a member selected from the group consisting of a hydrogen atom, substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, substituted or nonsubstituted aryl group, substituted or nonsubstituted acyl group, substituted or nonsubstituted alkoxycarbonyl group, substituted or nonsubstituted aryloxycarbonyl group, and substituted or nonsubstituted carbamoyl group, or alternatively, R3 and R4 may bond together to form a ring structure; and
each of R11 to R15 independently represents a hydrogen atom or a substituent, and at least one of R11 to R15 represents xe2x80x94(L1)xe2x80x94(L2)nxe2x80x94R, wherein L1 represents a member selected from the group consisting of xe2x80x94CONHxe2x80x94, xe2x80x94NHCONHxe2x80x94, xe2x80x94NHCOOxe2x80x94, xe2x80x94NHCOxe2x80x94, xe2x80x94OCONHxe2x80x94, xe2x80x94NHxe2x80x94, xe2x80x94NRXxe2x80x94, xe2x80x94COOxe2x80x94, xe2x80x94OCOxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94NHSO2xe2x80x94, xe2x80x94SO2NHxe2x80x94, and xe2x80x94CH2xe2x80x94 (wherein the left side of each group binds to the benzene ring of formula (I), and RX represents an alkyl group), L2 represents xe2x80x94CH2CH2Oxe2x80x94 or xe2x80x94CH2CONHxe2x80x94 (wherein the left side of each group binds to L1), R represents an 8- to 40-carbon, branched-chain or straight-chain, nonsubstituted alkyl group, and n represents 0 when L1 is a group other than xe2x80x94Oxe2x80x94, n represents 1 when L1 is xe2x80x94Oxe2x80x94 and L2 is xe2x80x94CH2CONHxe2x80x94, and n represents an integer from 0 to 10 when L1 is xe2x80x94Oxe2x80x94 and L2 is xe2x80x94CH2CH2Oxe2x80x94,
provided that two or more groups of R11 to R15 are not simultaneously branched-chain or straight-chain, nonsubstituted alkyl groups.
(9) A method of reducing a magenta stain by containing a coupler represented by formula (II) below in a silver halide color photographic lightsensitive material: 
wherein
X represents a member selected from the group consisting of a hydrogen atom, halogen atom, 1- to 32-carbon alkoxy group, 6- to 32-carbon aryloxy group, 1- to 32-carbon alkylthio group, 6- to 32-carbon arylthio group, 2- to 32-carbon heterocyclic thio group, 2- to 32-carbon alkoxycarbonyloxy group, 7- to 32-carbon aryloxycarbonyloxy group, 1- to 32-carbon carbamoyloxy group, 3- to 32-carbon heterocyclic carbonyloxy group, 2- to 30-carbon alkylcarbonyloxy group, 7- to 30-carbon arylcarbonyloxy group, and 2- to 32-carbon, 5- or 6-membered nitrogen-containing heterocyclic group that bonds to the coupling active position with a nitrogen atom;
each of R1 and R2 represents an electron-attracting group having a Hammett""s substituent constant "sgr"p value of not less than 0.20, the sum of the "sgr"p values of R1 and R2 being not less than 0.65;
R3 represents a member selected from the group consisting of a substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, substituted or nonsubstituted aryl group, and substituted or nonsubstituted heterocyclic group, and R4 represents a member selected from the group consisting of a hydrogen atom, substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, substituted or nonsubstituted aryl group, substituted or nonsubstituted acyl group, substituted or nonsubstituted alkoxycarbonyl group, substituted or nonsubstituted aryloxycarbonyl group, and substituted or nonsubstituted carbamoyl group, or alternatively, R3 and R4 may bond together to form a ring structure; and
each of R11 to R15 independently represents a hydrogen atom or a substituent, and at least two of R11 to R15 represent branched-chain or straight-chain, nonsubstituted alkyl groups.
(10) The lightsensitive material described in item (1), wherein each substituent of the formula (I) is as follows:
X represents a member selected from the group consisting of a hydrogen atom, halogen atom, arylthio group, carbamoyloxy group, and heterocyclic carbonyloxy group; each of R1 and R2 independently represents a member selected from the group consisting of a cyano group, alkoxycarbonyl group, nitro group, arylsulfonyl group, carbamoyl group, and alkyl halide group; R3 and R4 bond together to form a ring structure; and one to three groups of R11 to R15 are xe2x80x94(L1)xe2x80x94(L2)nxe2x80x94R as defined in item (1), and the other R11 to R15 are hydrogen atoms.
(11) The lightsensitive material described in item (10), wherein each substituent of the formula (I) is as follows:
X represents a member selected from the group consisting of a hydrogen atom, halogen atom, and heterocyclic carbonyloxy group; R1 is a cyano group; R2 is a cycloalkoxycarbonyl group; R3 and R4 bond together to form a 6-membered ring structure; one group of R11 to R15 is a straight-chain or branched-chain, nonsubstituted alkyl group; and the other R11 to R15 are hydrogen atoms.
(12) The lightsensitive material described in item (11), wherein each substituent of the formula (I) is as follows:
X is a hydrogen atom; R1 is a cyano group; R2 is a cycloalkoxycarbonyl group; R3 and R4 bond together to form a 6-membered ring structure; one group of R11 to R15 is a straight-chain or branched-chain, nonsubstituted alkyl group; and the other R11 to R15 are hydrogen atoms.
(13) The lightsensitive material described in item (2), wherein each substituent of the formula (II) is as follows:
X represents a member selected from the group consisting of a hydrogen atom, halogen atom, arylthio group, carbamoyloxy group, and heterocyclic carbonyloxy group; each of R1 and R2 independently represents a member selected from the group consisting of a cyano group, alkoxycarbonyl group, nitro group, arylsulfonyl group, carbamoyl group, and alkyl halide group; R3 and R4 bond together to form a ring structure; and two or three groups of R11 to R15 are straight-chain or branched-chain, nonsubstituted alkyl groups, and the other R11 to R15 are hydrogen atoms.
(14) The lightsensitive material described in item (13), wherein each substituent of the formula (II) is as follows:
X represents a member selected from the group consisting of a hydrogen atom, halogen atom, and heterocyclic carbonyloxy group; R1 is a cyano group; R2 is a cycloalkoxycarbonyl group; R3 and R4 bond together to form a 6-membered ring structure; two or three groups of R11 to R15 are straight-chain or branched-chain, nonsubstituted alkyl groups, and the other R11 to R15 are hydrogen atoms.
(15) The lightsensitive material described in item (14), wherein each substituent of the formula (II) is as follows:
X is a hydrogen atom; R1 is a cyano group; R2 is a cycloalkoxycarbonyl group; R3 and R4 bond together to form a 6-membered ring structure; R11, R13 and R15 are straight-chain or branched-chain, nonsubstituted alkyl groups, and R12 and R14 are hydrogen atoms.
(16) The compound described in item (5), wherein each substituent of the formula (III) is as follows:
X represents a member selected from the group consisting of a hydrogen atom, halogen atom, arylthio group, carbamoyloxy group, and heterocyclic carbonyloxy group; each of R1 and R2 independently represents a member selected from the group consisting of a cyano group, alkoxycarbonyl group, nitro group, arylsulfonyl group, carbamoyl group, and alkyl halide group; R3 and R4 bond together to form a ring structure; and two or three groups of R11 to R15 are straight-chain or branched-chain, nonsubstituted alkyl groups, and the other R11 to R15 are hydrogen atoms.
(17) The compound described in item (16), wherein each substituent of the formula (III) is as follows:
X represents a member selected from the group consisting of a hydrogen atom, halogen atom, and heterocyclic carbonyloxy group; R1 is a cyano group; R2 is a cycloalkoxycarbonyl group; R3 and R4 bond together to form a 6-membered ring structure; two or three groups of R11 to R15 are straight-chain or branched-chain, nonsubstituted alkyl groups, and the other R11 to R15 are hydrogen atoms.
(18) The compound described in item (17), wherein each substituent of the formula (III) is as follows:
X is a hydrogen atom; R1 is a cyano group; R2 is a cycloalkoxycarbonyl group; R3 and R4 bond together to form a 6-membered ring structure; R11, R13 and R15 are straight-chain or branched-chain, nonsubstituted alkyl groups, and R12 and R14 are hydrogen atoms.
Additional objects and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out hereinafter.
The present invention will be described in detail below. A Hammett""s substituent constant "sgr"p value used in this specification will be briefly described below. The Hammett""s rule is an empirical rule proposed in 1935 by L. P. Hammett in order to quantitatively argue the effects of substituents on reaction or equilibrium of benzene derivatives. The rule is widely regarded as appropriate in these days. The substituent constants obtained by the Hammett""s rule include a "sgr"p value and "sgr"m value, and these values are described in a large number of general literature. For example, the values are described in detail in J. A. Dean ed., xe2x80x9cLange""s Handbook of Chemistryxe2x80x9d, the 12th edition, 1979 (McGraw-Hill) and xe2x80x9cThe Extra Number of The Domain of Chemistryxe2x80x9d, Vol. 122, pp. 96 to 103, 1979 (Nanko Do), the disclosures of which are incorporated herein by reference. In the present invention, each substituent is restricted or explained by the Hammett""s substituent constant "sgr"p. However, this does not mean that the present invention is limited to substituents having the already known values found in these literature. That is, the present invention includes, of course, substituents having values that fall within the above range when measured on the basis of the Hammett""s rule even if they are unknown in literature. A compound represented by formula (I) or (II) of the present invention is not a benzene derivative. However, the "sgr"p value is used as a measure indicating the electron effect of a substituent, regardless of the substitution position.
In the present invention, the "sgr"p value will be used in this sense in the remainder of the text.
In this specification, a heterocyclic ring is a ring internally having a hetero atom and can also have aromatic nature. Examples of the hetero atom are N, S, O and P. This heterocyclic ring can further have a substituent. Also, substituents mentioned in this specification and substituents which an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group, and heterocyclic ring can have can be any substitutable groups unless specified otherwise. Examples of the substitutable groups are an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group, heterocyclic group, acyl group, acyloxy group, acylamino group, alkoxy group, aryloxy group, heterocyclic oxy group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxy carbonyl group, alkylcarbamoyl group, arylcarbamoyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfamoyl group, arylsulfamoyl group, alkylsulfonamide group, arylsulfonamide group, alkylamino group, arylamino group, alkylsulfinyl group, arylsulfinyl group, alkylthio group, arylthio group, mercapto group, hydroxy group, cyano group, nitro group, hydroxyamino group, and halogen atom.
A cyan coupler represented by formula (I) of the present invention will be described in detail below.
In formula (I), X represents a hydrogen atom, halogen atom, 1- to 32-carbon alkoxy group, 6- to 32-carbon aryloxy group, 1- to 32-carbon alkylthio group, 6- to 32-carbon arylthio group, 2- to 32-carbon heterocyclic thio group, 2- to 32-carbon alkoxycarbonyloxy group, 7- to 32-carbon aryloxycarbonyloxy group, 1- to 32-carbon carbamoyloxy group, 3- to 32-carbon heterocyclic carbonyloxy group, 2- to 30-carbon alkylcarbonyloxy group, 7- to 30-carbon arylcarbonyloxy group, or 2- to 32-carbon, 5- or 6-membered nitrogen-containing heterocyclic group that bonds to the coupling active position with a nitrogen atom.
X is preferably a hydrogen atom, halogen atom (e.g., a chlorine atom and bromine atom), arylthio group, carbamoyloxy group, or heterocyclic carbonyloxy group. X is further preferably a hydrogen atom or heterocyclic carbonyloxy group, and most preferably, a hydrogen atom.
A cyan coupler of the present invention forms a cyan image because both R1 and R2 are electron-attracting groups having "sgr"p values of 0.20 or more and the sum of the "sgr"p values of R1 and R2 is 0.65 or more. The sum of the "sgr"p values of R1 and R2 is preferably 0.70 or more, and the upper limit is about 2.0.
Each of R1 and R2 is an electron-attracting group having a Hammett""s substituent constant "sgr"p value of 0.20 or more, preferably 0.30 or more. The upper limit of the "sgr"p value is 1.0 or less.
Practical examples of an electron-attracting group having a "sgr"p value of 0.20 or more represented by R1 and R2 are an acyl group, acyloxy group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, alkyl halide group, alkoxy halide group, aryloxy halide group, alkylamino halide group, alkylthio halide group, aryl group which is substituted by another electron attracting group having a "sgr"p value of 0.20 or more, heterocyclic group, halogen atom, azo group, and selenocyanate group.
Of groups represented by R1 and R2, those which can further have substituents can further have substituents such as a halogen atom, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro group, carboxy group, sulfo group, amino group, alkoxy group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl group, and acyl group.
More specific examples of substituents of R1 and R2 are
a halogen atom (e.g., a chlorine atom and bromine atom),
alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group (e.g., a 1- to 32-carbon, straight-chain or branched-chain alkyl group, 7- to 38-carbon aralkyl group, 2- to 32-carbon alkenyl group, 2- to 32-carbon, straight-chain or branched-chain alkynyl group, 3- to 32-carbon, straight-chain or branched-chain cycloalkyl group, and 3- to 32-carbon, straight-chain or branched-chain cycloalkenyl group; more specifically, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-(3-pentadecylphenoxy)propyl, 3-{4-{2-[4-(4-hydroxyphenylsulfonyl)phenoxy]dodecaneamido}phenyl}propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, 3-(2,4-di-t-amylphenoxy)propyl, vinyl, allyl, 1-propenyl, and 2-pentenyl),
aryl group (e.g., phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, and 4-tetradecaneamidophenyl),
heterocyclic group (e.g., imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, and 2-benzothiazolyl),
cyano group,
hydroxy group,
nitro group,
carboxy group,
sulfo group,
amino group,
alkoxy group (e.g., methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy, and 2-methanesulfonylethoxy),
aryloxy group (e.g., phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, and 3-methoxycarbamoylphenoxy),
acylamino group (e.g., acetamide, benzamide, tetradecaneamide, 2-(2,4-di-t-amylphenoxy)butaneamide, 4-(3-t-butyl-4-hydroxyphenoxy)butaneamide, and 2-{4-(4-hydroxyphenylsulfonyl)phenoxy}decaneamide),
alkylamino group (e.g., methylamino, butylamino, dodecylamino, diethylamino, and methylbutylamino),
anilino group (e.g., phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, and 2-chloro-5-{2-(3-t-butyl-4-hydroxyphenoxy)dodecaneamido}anilino),
ureido group (e.g., phenylureido, methylureido, and N,N-dibutylureido),
sulfamoylamino group (e.g., N,N-dipropylsulfamoylamino, and N-methyl-N-decylsulfamoylamino),
alkylthio group (e.g., methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, and 3-(4-t-butylphenoxy)propylthio), arylthio group (e.g., phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, and 4-tetradecaneamidophenylthio),
alkoxycarbonylamino group (e.g., methoxycarbonylamino and tetradecyloxycarbonylamino),
sulfonamide group (e.g., methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, and 2-methoxy-5-t-butylbenzenesulfonamide),
carbamoyl group (e.g., N-ethylcarbamoyl, N,N-dibutylcarbamoyl, N-(2-dodecyloxyethyl)carbamoyl, N-methyl-N-dodecylcarbamoyl, and N-{3-(2,4-di-t-amylphenoxy)propyl}carbamoyl),
sulfamoyl group (e.g., N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-(2-dodecyloxyethyl)sulfamoyl, N-ethyl-N-dodecylsulfamoyl, and N,N-diethylsulfamoyl),
sulfonyl group (e.g., methanesulfonyl, octanesulfonyl, benzenesulfonyl, and toluenesulfonyl),
alkoxycarbonyl group (e.g., methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, and octadecyloxycarbonyl),
heterocyclic oxy group (e.g., 1-phenyltetrazole-5-oxy and 2-tetrahydropyranyloxy),
azo group (e.g., phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, and 2-hydroxy-4-propanoylphenylazo),
acyloxy group (e.g., acetoxy),
carbamoyloxy group (e.g., N-methylcarbamoyloxy and N-phenylcarbamoyloxy),
silyloxy group (e.g., trimethylsilyloxy and dibutylmethylsilyloxy),
aryloxycarbonylamino group (e.g., phenoxycarbonylamino),
imide group (e.g., N-succinimide, N-phthalimide, and 3-octadecenylsuccinimide),
heterocyclic thio group (e.g., 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, and 2-pyridylthio),
sulfinyl group (e.g., dodecanesulfinyl, 3-pentadecylphenylsulfinyl, and 3-phenoxypropylsulfinyl),
phosphonyl group (e.g., phenoxyphosphonyl, octyloxyphosphonyl, and phenylphosphonyl),
aryloxycarbonyl group (e.g., phenoxycarbonyl), and
acyl group (e.g., acetyl, 3-phenylpropanoyl, benzoyl, and 4-dodecyloxybenzoyl).
Note that in each of R1 and R2, alkyl of a group having an alkyl portion means straight-chain or branched-chain alkyl or cycloalkyl. Note also that substituted alkyl groups include aralkyl, alkenyl, alkynyl, and cycloalkenyl.
Accordingly, an alkoxycarbonyl group includes a straight-chain or branched-chain alkoxycarbonyl group, aralkyloxycarbonyl group, alkenyloxycarbonyl group, alkynyloxycarbonyl group, cycloalkoxycarbonyl group, and cycloalkenoxycarbonyl group.
R1 and R2 will be described in more detail below. Examples of an electron-attracting group having a "sgr"p value of 0.20 or more are
an acyl group (e.g., acetyl, 3-phenylpropanoyl, benzoyl, and 4-dodecyloxybenzoyl),
acyloxy group (e.g., acetoxy),
carbamoyl group (e.g., carbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl, N,N-dibutylcarbamoyl, N-(2-dodecyloxyethyl)carbamoyl, N-(4-n-pentadecaneamido)phenylcarbamoyl, N-methyl-N-dodecylcarbamoyl, and N-{3-(2,4-di-t-amylphenoxy)propyl}carbamoyl),
alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, iso-propyloxycarbonyl, tert-butyloxycarbonyl, iso-butyloxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl, and cyclohexenoxycarbonyl),
aryloxycarbonyl group (e.g., phenoxycarbonyl),
cyano group,
nitro group,
dialkylphosphono group (e.g., dimethylphosphono),
diarylphosphono group (e.g., diphenylphosphono),
diarylphosphinyl group (e.g., diphenylphosphinyl),
alkylsulfinyl group (e.g., 3-phenoxypropylsulfinyl),
arylsulfinyl group (e.g., 3-pentadecylphenylsulfinyl),
alkylsulfonyl group (e.g., methanesulfonyl and octanesulfonyl),
arylsulfonyl group (e.g., benzenesulfonyl and toluenesulfonyl),
sulfonyloxy group (e.g., methanesulfonyloxy and toluenesulfonyloxy),
acylthio group (e.g., acetylthio and benzoylthio),
sulfamoyl group (e.g., N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-(2-dodecyloxyethyl)sulfamoyl, N-ethyl-N-dodecylsulfamoyl, and N,N-diethylsulfamoyl),
thiocyanate group,
thiocarbonyl group (e.g., methylthiocarbonyl and phenylthiocarbonyl),
alkyl halide group (e.g., trifluoromethane and heptafluoropropane),
alkoxy halide group (e.g., trifluoromethyloxy),
aryloxy halide group (e.g., pentafluorophenyloxy),
alkylamino halide group (e.g., N,N-di-(trifluoromethyl)amino),
alkylthio halide group (e.g., difluoromethylthio and 1,1,2,2-tetrafluoroethylthio),
aryl group which is substituted by another electron-attracting group having a "sgr"p value of 0.20 or more (e.g., 2,4-dinitrophenyl, 2,4,6-trichlorophenyl, and pentachlorophenyl),
heterocyclic group (e.g., 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-benzimidazolyl, 5-chloro-1-tetrazolyl, and 1-pyrrolyl),
halogen atom (e.g., chlorine atom and bromine atom),
azo group (e.g., phenylazo), and
selenocyanate group.
Of these substituents, those which can further have substituents can further have substituents as described above.
Preferred examples of R1 and R2 are a 2- to 32-carbon acyl group, 2- to 32-carbon acyloxy group, 1- to 32-carbon carbamoyl group, 2- to 32-carbon alkoxycarbonyl group, 7- to 32-carbon aryloxycarbonyl group, cyano group, nitro group, 1- to 32-carbon alkylsulfinyl group, 6- to 32-carbon arylsulfinyl group, 1- to 32-carbon alkylsulfonyl group, 6- to 32-carbon arylsulfonyl group, 0- to 32-carbon sulfamoyl group, 1- to 32-carbon alkyl halide group, 1- to 32-carbon alkoxy halide group, 1- to 32-carbon alkylthio halide group, 7- to 32-carbon aryloxy halide group, 7- to 32-carbon aryl group substituted by two or more another electron-attracting groups having ap values of 0.20 or more, and 5- to 8-membered, 1- to 36-carbon heterocyclic group having a nitrogen atom, oxygen atom, or sulfur atom.
More Preferred examples of R1 and R2 are 2- to 32-carbon alkoxycarbonyl group, nitro group, cyano group, 6- to 32-carbon arylsulfonyl group, 1- to 32-carbon carbamoyl group, and 1- to 32-carbon alkyl halide group. R1 is most preferably a cyano group. R2 is particularly preferably a 2- to 32-carbon alkoxycarbonyl group, and most preferably, a 4- to 32-carbon cycloalkoxycarbonyl group.
In formula (I), R3 represents a substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, substituted or nonsubstituted aryl group, or substituted or nonsubstituted heterocyclic group.
More specifically, an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, and cycloalkenyl group represented by R3 are a 1- to 32-carbon, straight-chain or branched-chain alkyl group, 7- to 32-carbon aralkyl group, 2- to 32-carbon alkenyl group, 2- to 32-carbon alkynyl group, 3- to 32-carbon cycloalkyl group, and 3- to 32-carbon cycloalkenyl group. Practical examples are methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-(3-pentadecylphenoxy)propyl, 3-{4-{2-[4-(4-hydroxyphenylsulfonyl)phenoxy]dodecaneamido}phenyl}propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, 3-(2,4-di-t-amylphenoxy)propyl, vinyl, allyl, 1-propenyl, and 2-pentenyl. An aryl group represented by R3 is preferably a 6- to 36-carbon aryl group, and a monocyclic group is more preferable. Practical examples are phenyl, 4-t-butylphenyl, 2-methylphenyl, 2,4,6-trimethylphenyl, 2-methoxyphenyl, 4-methoxyphenyl, 2,6-dichlorophenyl, 2-chlorophenyl, and 2,4-dichlorophenyl. A heterocyclic group represented by R3 is preferably a 5- to 8-membered, 1- to 36-carbon heterocyclic group having a nitrogen atom, oxygen atom, or sulfur atom. A heterocyclic group is more preferably a 5- or 6-membered ring bonded by a nitrogen atom. These rings can also form a condensed ring together with a benzene ring or a hetero ring. Practical examples are imidazolyl, pyrazolyl, triazolyl, piperidino, pyrrolidyl, pyrrolyl, morpholino, pyrazolidyl, and thiazolidyl, and pyrrolidyl is preferable.
Of these substituents, those which can further have substituents can be further substituted by substituents enumerated for R1 and R2 described above.
Preferred examples of R3 are a substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, and substituted or nonsubstituted cycloalkenyl group.
Examples of group represented by R4 are a substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, substituted or nonsubstituted aryl group, substituted or nonsubstituted acyl group, substituted or nonsubstituted alkoxycarbonyl group, substituted or nonsubstituted aryloxycarbonyl group, and substituted or nonsubstituted carbamoyl group.
More specifically, a hydrogen atom, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, and cycloalkenyl group represented by R4 are a 1- to 32-carbon, straight-chain or branched-chain alkyl group, 7- to 32-carbon aralkyl group, 2- to 32-carbon alkenyl group, 2- to 32-carbon alkynyl group, 3- to 32-carbon cycloalkyl group, and 3- to 32-carbon cycloalkenyl group. Practical examples are methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-(3-pentadecylphenoxy)propyl, 3-{4-{2-[4-(4-hydroxyphenylsulfonyl)phenoxy]dodecaneamido}phenyl}propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, 3-(2,4-di-t-amylphenoxy)propyl, vinyl, allyl, 1-propenyl, and 2-pentenyl. An aryl group represented by R4 is preferably a 6- to 36-carbon aryl group, and a monocyclic group is more preferable. Practical examples are phenyl, 4-t-butylphenyl, 2-methylphenyl, 2,4,6-trimethylphenyl, 2-methoxyphenyl, 4-methoxyphenyl, 2,6-dichlorophenyl, 2-chlorophenyl, and 2,4-dichlorophenyl. An acyl group represented by R4 is preferably a 2- to 32-carbon acyl group. Practical examples are acetyl, pivaloyl, octanoyl, and benzoyl. Examples of an alkoxycarbonyl group, aryloxycarbonyl group, and carbamoyl group are those described above as groups which substitute R1 and R2.
Of these substituents, those which can further have substituents can be further substituted by substituents enumerated as groups which substitute R1 and R2 described above.
Preferred examples of R4 are a substituted or nonsubstituted alkyl group, substituted or nonsubstituted alkenyl group, substituted or nonsubstituted alkynyl group, substituted or nonsubstituted cycloalkyl group, substituted or nonsubstituted cycloalkenyl group, and substituted or nonsubstituted aryl group.
R3 and R4 can bond to form a 5- or 6-membered ring bonded by a nitrogen atom. Practical examples are imidazolyl, pyrazolyl, triazolyl, piperidyl, piperidino, pyrrolidinyl, pyrrolyl, morpholyl, morpholino, pyrazolidinyl, thiazolidinyl, pyrazolinyl, and piperadinyl. These rings can form a condensed ring together with a benzene ring or a hetero ring.
As R3 and R4, substituents which form a ring structure are preferred to those which do not. Of these substituents, groups forming a 6-membered ring bonded by a nitrogen atom are preferable. Of these groups, morpholino, piperadinyl substituted by an acyl group, piperidino, and piperidino substituted by a carboxyl group are preferable.
In formula (I), each of R11 to R15 independently represents a hydrogen atom or a substituent, and at least one of R11 to R15 is xe2x80x94(L1)xe2x80x94(L2)xe2x80x94R. L1 represents a group selected from xe2x80x94CONHxe2x80x94, xe2x80x94NHCONHxe2x80x94, xe2x80x94NHCOOxe2x80x94, xe2x80x94NHCOxe2x80x94, xe2x80x94OCONHxe2x80x94, xe2x80x94NHxe2x80x94, xe2x80x94NRxxe2x80x94, xe2x80x94COOxe2x80x94, xe2x80x94OCOxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94NHSO2xe2x80x94, xe2x80x94SO2NHxe2x80x94, and xe2x80x94CH2xe2x80x94 (wherein the left side of each group binds to the benzene ring of formula (I)). L2 represents xe2x80x94CH2CH2Oxe2x80x94 or xe2x80x94CH2CONHxe2x80x94 (wherein the left side of each group binds to L1). R represents an 8- to 40- carbon, branched-chain or straight-chain, nonsubstituted alkyl group. Further, Rx denotes a 1- to 32-carbon alkyl group. However, n represents 0 when L1 is a group other than xe2x80x94Oxe2x80x94, and n represents 1 when L1 is xe2x80x94Oxe2x80x94 and L2 is xe2x80x94CH2CONHxe2x80x94. Further, when L1 is xe2x80x94Oxe2x80x94 and L2 is xe2x80x94CH2CH2Oxe2x80x94, n represents an integer of 0 to 10. However, it excludes the case where two or more groups of R11 to R15 are branched-chain or straight-chain, nonsubstituted alkyl groups.
In the substituent xe2x80x94(L1)xe2x80x94(L2)nxe2x80x94R which is included as at least one of R11 to R15 in formula (I), R is an 8- to 40-carbon, branched-chain or straight-chain, nonsubstituted alkyl group, such as n-nonyl group, sec-nonyl group, t-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-hexadecyl group, and n-octadecyl group, etc.
In formula (I), examples of each group represented by R11 to R15 are a halogen atom, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro group, carboxy group, sulfo group, amino group, alkoxy group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl group, and acyl group.
In formula (I), practical examples of each group represented by R11 to R15 are groups described above as groups which substitute R1 and R2.
Of these substituents, those which can further have substituents can be further substituted by substituents enumerated as groups which substitute R1 and R2 described above.
Preferred examples of each group represented by R11 to R15 are a hydrogen atom, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group, heterocyclic group, cyano group, nitro group, alkoxy group, acylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group (alkylsulfonylamino group and arylsulfonylamino group), carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl group, acyl group, and halogen atom.
Each of R11 to R15 is more preferably a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, carbamoyl group, sulfamoyl group, sulfonamide group (alkylsulfonylamino group and arylsulfonylamino group), or halogen atom. Each of R11 to R15 is most preferably a hydrogen atom, alkyl group, 6- to 40-carbon, substituted or nonsubstituted alkoxy group, 1- to 32-carbon sulfamoyl group, or 1- to 32-carbon sulfonamide group (alkylsulfonylamino group and arylsulfonylamino group).
A preferred combination as a cyan coupler represented by formula (I) of the present invention is: X is a hydrogen atom, halogen atom, arylthio group, carbamoyloxy group, or heterocyclic carbonyloxy group; each of R1 and R2 independently represents a group selected from a cyano group, alkoxycarbonyl group, nitro group, arylsulfonyl group, carbamoyl group, and alkyl halide group; R3 and R4 form a ring structure; and one to three groups of R11 to R15 are xe2x80x94(L1)xe2x80x94(L2)nxe2x80x94R as defined above, and the other R11 to R15 are hydrogen atoms.
A further preferred combination as a cyan coupler represented by formula (I) is: X is a hydrogen atom, halogen atom, or heterocyclic carbonyloxy group; R1 is a cyano group; R2 is a cycloalkoxycarbonyl group; R3 and R4 form a 6-membered ring structure; one group of R11 to R15 is a straight-chain or branched-chain, nonsubstituted alkyl group; and the other R11 to R15 are hydrogen atoms.
A most preferred combination as a cyan coupler represented by formula (I) is: X is a hydrogen atom; R1 is a cyano group; R2 is a cycloalkoxycarbonyl group; R3 and R4 form a 6-membered ring structure; one group of R11 to R15 is a straight-chain or branched-chain, nonsubstituted alkyl group; and the other R11 to R15 are hydrogen atoms.
Next, a cyan coupler represented by formula (II) of the present invention will now be described in detail. In formula (II), substituents represented by R1, R2, X, R3 and R4 are the same as the substituents specified in formula (I). Further, each of R11 to R15 independently represents a hydrogen atom or a substituent specified by R11 to R15 in above formula (I). At least two of these substituents are a branched-chain or straight-chain, nonsubstituted alkyl group. The alkyl group preferably has 1- to 40-carbon atoms.
Examples of a 1- to 40-carbon, branched-chain or straight-chain, nonsubstituted alkyl group which is included as at least two of R11 to R15 in formula (II) are a methyl group, ethyl group, n-propyl group, iso-propyl group, cyclopropyl group, n-butyl group, sec-butyl group, iso-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, sec-nonyl group, t-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-hexadecyl group, and n-octadecyl group, etc.
A preferred combination as a cyan coupler represented by formula (II) of the present invention is: X is a hydrogen atom, halogen atom, arylthio group, carbamoyloxy group, or heterocyclic carbonyloxy group; each of R1 and R2 independently represents a group selected from a cyano group, alkoxycarbonyl group, nitro group, arylsulfonyl group, carbamoyl group, and alkyl halide group; R3 and R4 form a ring structure; and two or three groups of R11 to R15 are straight-chain or branched-chain, nonsubstituted alkyl groups, and the other R11 to R15 are hydrogen atoms.
A further preferred combination as a cyan coupler represented by formula (II) is: X is a hydrogen atom, halogen atom, or heterocyclic carbonyloxy group; R1 is a cyano group; R2 is a cycloalkoxycarbonyl group; R3 and R4 form a 6-membered ring structure; two or three groups of R11 to R15 are straight-chain or branched-chain, nonsubstituted alkyl groups, and the other R11 to R15 are hydrogen atoms.
A most preferred combination as a cyan coupler represented by formula (II) is: X is a hydrogen atom; R1 is a cyano group; R2 is a cycloalkoxycarbonyl group; R3 and R4 form a 6-membered ring structure; R11, R13 and R15 are straight-chain or branched-chain, nonsubstituted alkyl groups, and R12 and R14 are hydrogen atoms.
Next, a compound represented by formula (III) of the present invention will now be described. In formula (III), X represents a hydrogen atom, halogen atom, 1- to 32-carbon alkoxy group, 6- to 32-carbon aryloxy group, 1- to 32-carbon alkylthio group, 6- to 32-carbon arylthio group, 2- to 32-carbon heterocyclic thio group, 2- to 32-carbon alkoxycarbonyloxy group, 7- to 32-carbon aryloxycarbonyloxy group, 1- to 32-carbon carbamoyloxy group, 3- to 32-carbon heterocyclic carbonyloxy group, 2- to 30-carbon alkylcarbonyloxy group, 7- to 30-carbon arylcarbonyloxy group, and 2- to 32-carbon, 5- or 6-membered nitrogen-containing heterocyclic group that bonds to the 5-position of the 1H-pyrrolo-[1,2-b][1,2,4]triazole ring with a nitrogen atom. In formula (III), substituents represented by R1, R2, R3, R4, and R11 to R15 have the same meaning as those of formula (II). A preferred combination of substituents in a compound represented by formula (III) of the present invention is the same as the preferred combination described in formula (II).
To make a silver halide photosensitive material, preferably a red-sensitive silver halide emulsion layer to contain a cyan coupler of the present invention, the use of a so-called incorporated coupler is preferable. For this purpose, at least one group of R11, R12, R13, R14, R15, and X is preferably a so-called ballast group (having a total number of carbon atoms of preferably 10 or more). The total number of carbon atoms of the ballast group is more preferably 10 to 50. Particularly preferably, at least one group of R11, R12, R13, R14, and R15 has a ballast group.
Practical examples of cyan couplers and pyrrolotriazole compounds defined by the present invention will be presented below. However, the present invention is not limited to these examples.
A lightsensitive material of the present invention has at least one layer containing a coupler defined by the present invention on a support. 
Compounds represented by formulae (I) and (II) can be synthesized by the following method.